Oxadiazole based photosensitizers for use in dye-sensitive solar cells and photodynamic therapy

ABSTRACT

An oxadiazole dye for use as an organic photosensitizer. The oxadiazole dye comprising donor-π-spacer-acceptor type portions in which at least one of an oxadiazole isomer acts as a π-conjugated bridge (spacer), a biphenyl unit acts as an electron-donating unit, a carboxyl group act as an electron acceptor group, and a cyano group acts as an anchor group. An optional thiophene group acts as part of the π-conjugated bridge (spacer). The dye for use as organic photosensitizers in a dye-sensitized solar cell and in photodynamic therapies. Computational DFT and time dependent DFT (TD-DFT) modeling techniques showing Light Harvesting Efficiency (LHE), Free Energy for Electron Injection (ΔG inject ), Excitation Energies, and Frontier Molecular Orbitals (FMOs) indicate that the series of dye comprise a more negative ΔG inject  and a higher LHE value; resulting in a higher incident photon to current efficiency (IPCE).

FIELD OF THE INVENTION

The present invention relates to organic light absorbing compoundscomprising at least one substituted oxadiazole group and dye sensitizedsolar cells containing one or more of the light absorbing compounds. Theinvention includes the use of the organic light absorbing compounds asphotosensitizers, or dyes, in a dye sensitized photoelectrictransformation element such as a dye-sensitized solar cell (DSSC). Theinvention includes the use of the organic light absorbing compounds as aphotosensitizer in a photodynamic therapy process.

BACKGROUND OF THE INVENTION

The “background” description provided herein is for the purpose ofgenerally presenting the context of the disclosure. Work of thepresently named inventors, to the extent it is described in thisbackground section, as well as aspects of the description which may nototherwise qualify as prior art at the time of filing, are neitherexpressly or impliedly admitted as prior art against the presentinvention.

Dye Sensitized Solar Cells (DSSCs), developed by O'Regan and Gratzel in1991, are third-generation photovolatic devices which offer increasedphotoelectric transformation efficiencies at a low monetary cost. Incontrast to silicon-based photovoltaic systems, where a semiconductorassumes both the tasks of light absorption and charge carrier transport,the configuration of a dye sensitized solar cell separates thesefunctions.

Dye Sensitized Solar Cells (DSSCs) are unique in their functions in thatthey mimic the naturally occurring photosynthetic process found inplants and green algae. DSSCs utilize chromophores, similar to aphotosynthetic system's porphyrins, in order to generate photosensitivecharges which convert sunlight to energy. When subjected to light of anappropriate wavelength, these chromophores, as part of a dye molecule,are photochemically excited, and serve as the basis for conversion ofsunlight into electrical energy.

Structurally, a dye sensitized solar cell (DSSC) has four maincomponents which include 1) an optically transparent electrode (anode);2) an organic, or organometallic, molecule (known as a dye orphotosensitizer) adsorbed on a semiconductor oxide; 3) a liquidinorganic electrolyte or a solid organic bole-transporting material; and4) a counter-electrode (cathode). The anode and cathode are arranged ina sandwich-like configuration, and the electrolyte is inserted betweenthe two electrodes.

For a DSSC to operate the dye must allow electrons to move to an orbitalwith a higher energy (a dye excited state). The movement of theseelectrons result in the occurrence of a charge separation at theinterface of the dye (now sensitized) and the semiconductor oxidecomponents. This charge separation occurs via a photo-induced electroninjection from the dye into the conduction band of the semiconductoroxide (i.e. titanium dioxide), leaving the dye molecules in an oxidizedform. The electrons are then collected on a transparent conductivelayer, and reach the counter-electrode (cathode) through an externalelectric circuit. The oxidized molecules of the dye are then regeneratedthrough a transfer, such as one catalyzed by platinum (Pt), deposited ona cathode. Herein, the electrons trigger a series of redox reactionsmediated through a redox pair which acts as an electrolyte. At the endof the reactions, the redox pair, now in a reduced form, transfers anelectron to the dye, (which was held in an oxidized form), subsequentlyregenerating it and closing the cycle.

In addition to their reduced production costs and potential forachieving high energy-conversion efficiencies (η). Dye sensitized solarcells (DSSCs) have also attracted considerable attention for theirflexibility, semi-transparency, and stability during both prolongedlight and thermal stresses. DSSCs have a greater independence on theangle of incident light needed to operate, as well as a high response tolow level lighting conditions. As such, DSSCs tend to outperformconventional silicon photovoltaic devices under diffuse lightingconditions, such as those found in shady areas, on cloudy and/or rainydays, or even indoors with ambient lighting conditions. Indoorapplications for DSSCs include their incorporation into a variety ofdevices such as, but not limited to, cell phones, laptop computers, andipads. DSSCs may also be utilized in conventional solar arrays, or forbuilding-integrated photovoltaic products such as windows, skylights,solar tubes, and siding.

For solar cells to attain the desired high level of photoelectrictransformation efficiency (η), the dye component should possess a wideabsorption spectrum (of solar light), as well as a high molar extinctioncoefficient (ε). Consequently, photoelectric transformation efficiencyis primarily determined by the number of collected and injected photons,and thus by the light absorbed by the dye or photosensitizer.Additionally, for an efficient electron injection, the dye must be ableto absorb (by chemisorption) onto the surface of the semiconductor, andupon photoexcitation, inject electrons into the conduction band of thesemiconductor with a quantum yield of unity. As known in the art, the‘quantum yield of unity’ is useful in modeling photosynthesis, whereQ_(D)=Q_(A)=1.

Currently, the most successful and widely-used dyes are organometalliccompounds based on ruthenium 2⁺ complexes [Ru(II)]. These dyes haveallowed photoelectric transformation efficiencies (η) of 11% to bereached. However, despite their efficiency, ruthenium compounds have avariety of disadvantages. One concern is the low molar extinctioncoefficient (ε) inherent to derivatives of ruthenium [Ru(II)]. Othershortcomings involve the expensive and complex synthesis andpurification phases which ultimately result in a product having alimited chemical stability.

Further still, the photo-active regions of photovoltaic devicesemploying ruthenium complex dyes are reduced to the visible part of thesolar spectrum, and within that, to the shorter wavelength regions.Consequently, photons of the longer wavelength regions are notharvested, and cannot be converted into electrical energy. Therefore, itis desirable to extend the photo-response of a dye into the longerwavelength regions of the solar spectrum so as to improve the overalllight-to-electricity conversion efficiency of a DSSC. As syntheticmodifications of ruthenium complexes have been carried out with limitedsuccess, the development of alternative dyes with wider absorption bandsfalling within the longer wavelength regions of the solar spectrum hasgarnered a greater interest.

Metal-free organic dyes present one such alternative dye. As a group,they present advantages over organometallic dyes for use in DSSCsincluding, but not limited to: (1) possessing high molar extinctioncoefficients (ε), (2) having simpler and less expensive synthesisprocesses, and (3) the existence of a chemical industry already capableof carrying out a large scale synthesis process.

The structural arrangement of metal-free organic dye sensitizers is mostoften of the linear D-π-A type. Therein, ‘D’ is an electron donor group(i.e. electron-rich), ‘π’ is an unsaturated spacer having π-conjugatedbonds and ‘A’ is an electron acceptor group (i.e. electron-poor group).Customarily, the electron acceptor group is further coupled with a groupwhich allows for the anchoring (i.e. adsorption) of the dye moleculeonto a surface such as titanium dioxide. The D-π-A system allows for avariety of modifications to be made to the dye by varying the D,π-spacer, and/or A groups.

For most metal-free organic dyes, arylamine derivatives function as theelectron-donor group (D). These typically include groups of thetriarylamine type (NAr₃). A cyanoacrylic acid or rhodamine residuetypically functions as an electron acceptor group A, while the π spaceris often based on thiophene structures, such as a fused monocyclicand/or polycyclic thiophene ring(s). With regard to the anchoring group,many organic dyes reporting good efficiencies have an anchoring groupcomprising an acrylic acid group. Often, a combination of the electronacceptor group ‘A’ and the anchor group include a 2-cyanoacrylate group.However, in the design of functional and efficient dye molecules, othergroups should be considered for the D, π, and A groups.

The electrical and optical properties of π-conjugated organic moleculesare linked to a parameter known as the HOMO-LUMO gap (Eg). Thiscorresponds to the energy difference between the Highest OccupiedMolecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital(LUMO). The energy difference between the HOMO and LUMO levels isapproximately equal to the ‘band gap energy’ as defined for collectionsof molecules in a thin-film. This difference in value, given relative tothe Fermi level and in units of Hartree, may serve as a measure of theexcitability of a molecule. For example, the smaller the energy, themore easily the molecule will be excited. In order to be used inoptoelectronics, including DSSCs, or photodynamic therapies, this bandgap energy should be as low as possible.

It is also important to realize that many molecules presenting a low Eggap are often those in possession of higher dimensions. These ‘highdimension molecules’ tend to, by virtue of their bulky structure, beweakly soluble, thus limiting their role in photovoltaic devices.Additionally, larger dimension molecules have been associated withgreater toxicity, or health, risks to those individuals exposed to them.Therefore, it is important to find new light absorbing π-conjugatedmolecules (D-π-A) that present a low Eg gap, are soluble in a preferredsolvent (i.e. an organic medium and/or water), and are non-toxic tohumans and animals.

In summary, an important strategy for realizing a high photoelectricconversion efficiency is to allow for light of a long wavelength to beabsorbed by the dye molecule, along with chromophore and π spacer groupcombinations which render a low HOMO-LUMO gap in the dye molecule aswell.

In order to evaluate any proposed dye candidates, their properties, suchas ‘band-gap energy’ should be determined. Dye energies, based upon theHOMO and LUMO value, can be established experimentally by means ofcyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS) orultraviolet photoelectron spectroscopy (UPS). Dye energies can also becalculated by means of quantum-mechanical methods, for example, by meansof dependent density functional theory and/or time-dependent densityfunctional theory (DFT/TD-DFT). Theoretical DFT/TD-DFT can suggest whichdyes will have the greatest efficiencies prior to exploration ofsynthesis routes. Therefore, investigation into alternative D, π-spacer,and A groups is proceeding, with both theoretical and physicalapproaches, in order to determine dye energies and light harvestingefficiencies of candidate dye molecules.

In this regard, density functional theory/time dependent densityfunctional theory (DFT/TD-DFT) is an effective tool for investigatingthe ground and excited state properties of photosensitizer complexes ascompared to other high level quantum approaches. The DFT approach is, inprinciple, exact, with DFT/TD-DFT computed orbitals deemed suitable fora typical molecular orbital theoretical analysis and interpretation.Furthermore, DFT/TD-DFT fundamental scaling properties do notdeteriorate when the methodological precision is increased.

Most dyes absorb light in the same range as a commonly used red-dye(below 600 nm). Thus photons of the longer wavelength region(s) arestill lost to photoconversion. As the spectrum of solar radiation atground level has an emission peak that extends from approximately 500 nmto approximately 650 nm, the use of dyes that have absorption peaks inthis region of the spectrum are greatly needed. Dyes prepared to dateeither absorb below 500 nm, or above 650 nm, and therefore do notcapture most of the solar radiation. A second drawback is that thesedyes exhibit low molar extinction coefficients.

Other roles exist for light absorbing molecules, such as thosephotosensitizers which have been developed for DSSCs. These moleculesmay also play a role in treating medical conditions through a course oftreatment known as phototherapy. Photodynamic therapy involves aminimally invasive two-step process wherein a photosensitizer isadministered and, once it has permeated a target tissue, thephotosensitizer is then activated by exposure to a dose ofelectromagnetic (usually light) radiation at a particular wavelength.Photodynamic therapies have been used to treat a number of conditionsincluding the treatment of malignant skin cells, (ie basal cellcarcinoma), age-related macular degeneration, actinic keratosis and hairloss.

More specifically, photodynamic therapy (PDT) is a form of phototherapywhich uses nontoxic light-sensitive compounds that are exposedselectively to light, whereupon they cause a reduction in targetedhyperproliferative, malignant, and/or diseased cells. PTD may alsoresult in the stimulus of hair growth. Key requirements for the designof effective phototherapeutic agents include, but are not limited to,having an efficient energy or electron transfer to cellular components,a low tendency to aggregate when placed in a solvent delivery system, anefficient and selective targeting of a desired tissue, a low systemictoxicity, and a lack of mutagenicity.

One phototherapy mechanism pathway occurs via the direct energy orelectron transfer from a photosensitizer to a targeted cellularcomponent(s) thereby causing cellular death or necrosis. The wavelengthof the light source is required to be of an appropriate wavelength so asto excite the photosensitizer dye in order to destroy any tissues whichhave selectively taken up the photosensitizer and have been locallyexposed to light. Malignant and other diseased cells of the skin (i.e.the epidermal, dermal and hypodermal layers) are the most accessible tolight and can therefore be treated using photodynamic therapy with thegreatest ease. As red light has a penetration of about 1 cm in livingtissues, malignant and/or diseased cells on or near the surface of theskin can most preferably be treated with this wavelength of light.

Wavelengths of light in the near infrared region (NIR region 750 nm-950nm) provide radiation which penetrates more deeply in the skin.Therefore, in order to treat malignant or diseased tissues which requirea higher penetration of light into the body, the photosensitizer shouldabsorb in these higher wavelengths. Also, as with the use ofphotosensitizers for DSSCs, the HOMO-LUMO (Eg) gap of the dyemolecule(s) for use in a photodynamic therapy process should also be aslow as possible.

Therefore, there is a need to provide photosensitizers which areversatile, have a low HOMO-LUMO (Eg) gap, and absorb light in a widespectrum of wavelengths. Those compounds having absorption in thevisible, UV and/or NIR region, i.e. between 300 nm and 1000 nm aredesired. The development of dye compounds which absorb radiations from400 nm-950 mn is highly desirable due to the fact that this specificrange of absorbance enables the use of the dye compounds in the field ofelectronics, photovoltaics, optoelectronics and photodynamic therapies.An organic dye should also be resistant to photodegradation, and containa reactive group capable of binding the dye stably to a surface such asthat of a semiconductor, or in the case of phototherapy, a layer of theskin, so as to facilitate the transfer of electrons.

SUMMARY OF THE INVENTION

The present disclosure provides a light absorbing molecule, alsoreferred to herein as a light absorbing compound, a photosensitizer, anda “dye”, of the D-π-A (Donor-spacer-Acceptor) type and a dye sensitizedsolar cell (DSSC) containing the light absorbing molecule. The dye asdisclosed is an oxadiazole based photosensitizer for use, for example,in photovoltaic devices such as, but not limited to, dye-sensitivedsolar cells (DSSC). The dye provides a stable and soluble functionalcompound having absorption in the UV and visible wavelength regions ofthe solar spectrum. A dye as disclosed herein may be used individually,or combined with a second dye, as disclosed herein, or with other knowndyes, so as to cover a broad range of the solar spectrum. The lightabsorbing molecule disclosed herein may be tuned to provide a lowbandgap and favorable energy level, and can be efficiently chemisorbedto a nanoporous surface of a photoactive layer in a DSSC structure ordevice. In addition to its use in photovoltaic devices, the lightabsorbing molecule disclosed herein can be used in the fields ofoptoelectronics, photonics, and photodynamic therapies. In someembodiments the light absorbing molecule contains few atoms and absorbsin the longer wavelength regions of light thus presenting a goodphotodynamic therapy dye candidate. Photodynamic therapy may be usefulin treating a hyperprolifertive, cancerous, or diseased tissue.

In a first embodiment the light absorbing molecule of the presentdisclosure is an organic light absorbing molecule of formula (I),including the tautomers thereof:

wherein A₁ is a divalent thiophene group of formula (I′)

wherein R₁ is H, OH, C₁-C₆ alkyl, Cl, Br, F, or I, and n=1-5;A₂ is at least one divalent 5-membered heterocyclic group selected fromthe group consisting of

wherein m=1-5;A₃ is an aromatic hydrocarbon chromophore of formula (VI′)

wherein R₁ is H, OH, C₁-C₆ alkyl, Cl, Br, F, or I and p=1-3, and theterminal A₃ aryl group of the light absorbing molecule is bonded to oneother aryl group of formula (VI′) and a hydrogen atom. In otherembodiments of the invention the thiophenyl group of formula (I′) isoptional, e.g., n=0.

In a further embodiment the organic light absorbing molecule of thepresent disclosure may be in the form of an (E) or (Z) configurationisomer.

In a preferred embodiment the organic light absorbing molecule comprisesa substituted cyanoacrylic acid selected from the group consisting of:

-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (E)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (Z)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;

In a preferred embodiment the organic light absorbing molecule is asubstituted cyanoacrylic acid selected from the group consisting of:

-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid; and-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

including the tautomers thereof.

In a further embodiment, at least one of -A₁, or at least one of -A₁-A₂of formula (I), forms a conjugated system with the adjacent aromatichydrocarbon chromophore of formula (VI′).

In another embodiment the organic light absorbing molecule of formula(I) comprises a cyanoacrylic acid wherein a —COOH group of thecyanoacrylic acid is covalently coupled to a solid surface, for exampleas a —COO⁻ group.

In a further embodiment the surface is a photoactive semiconductorlayer, or a layer of an animal skin selected from the group consistingof an epidermis, a dermis and a hypodermis.

In a preferred embodiment the surface is a photoactive semiconductorlayer comprising titanium dioxide.

In a further embodiment the organic light absorbing molecule of formula(I) absorbs at least one wavelength of visible light or UV light.

In another embodiment the disclosure includes a dye sensitized solarsell comprising an organic light absorbing molecule of formula (I).

In a further embodiment the disclosure includes a dye having achromophore coupled to a conjugated system (see FIG. 4) wherein thechromophore is an organic moiety able to absorb UV and/or visible lightwhen coupled with a conjugated system selected from the group consistingof:

wherein R₁ is H, OH, C₁-C₆ alkyl, Cl, Br, F, or I and p is 1-3;

wherein the conjugated system comprises a divalent thiophene group offormula (I′)

wherein R₁ is H, OH, C₁-C₆ alkyl, Cl, Br, F, or I and n=0-5;

and at least one divalent 5-membered heterocyclic group selected fromthe group consisting of

wherein m=1-5;

wherein R₂ is H, —CN, and/or —NO₂, preferably —CN, and

wherein R₃ is —COOH, —SO₃H, —PO₃H₂, and/or —BO₂H₂, preferably —COOH.

In a further embodiment the chromophore has an independent absorption inthe range of 200-300 nm when uncoupled to the conjugated system; and afirst absorption in the wavelength range of 326 nm-500 nm, for exampleand including in the range of 350 nm-450 nm, and a second absorption inthe range of 472-700 nm, for example and including 500-650 nm whencoupled with the conjugated system.

In a further embodiment the dye is chemisorbed to a photoactivesemiconductor layer of a DSSC, or a dermal layer of an animal skinselected from the group consisting of an epidermis, a dermis and ahypodermis.

In a preferred embodiment the dye is chemisorbed to a photoactivesemiconductor layer comprising titanium dioxide.

In a further embodiment the disclosure includes a dye sensitizedphotoelectric transformation element comprising at least one organicdye.

In a third embodiment the disclosure includes a photoelectric conversiondevice comprising at least one of a passive substrate, wherein thepassive substrate comprises: a conductive layer;

a light-absorbing layer

an intermediate layer; and

a counter electrode;

-   -   further wherein the light absorbing layer preferably comprises        at least one selected from the group consisting of

-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;

-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;

-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;

-   (E)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;

-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

-   (E)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid; and

-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;

-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;

-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;

-   (Z)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;

-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

-   (Z)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

including the tautomers thereof.

In a still further embodiment the disclosure includes a compositioncomprising a pharmaceutically acceptable medium and an oxadiazolecompound selected from the group consisting of:

-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (E)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid; and-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (Z)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

including the tautomers thereof;

In a further embodiment the present disclosure includes a method ofphotodynamic therapy for treating a hypo- or hyper-proliferative,malignant and/or diseased tissue in a subject in need thereof,comprising: (i) administering to the hypo- or hyper-proliferative,malignant and/or diseased tissue of the subject an oxadiazole compoundselected from the group consisting of

-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (E)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (E)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid; and-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (Z)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;-   (Z)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylic    acid;

including the tautomers thereof and/or a pharmaceutically acceptableconjugate thereof, and (ii) irradiating the target tissue with a lightof a wavelength and intensity sufficient to activate the oxadiazolecompound, so as to destroy, or decrease in size, the hyperproliferative,malignant, and/or diseased tissue, or to stimulate a hypo-proliferativetissue.

In a further embodiment, the hypo- or hyper-proliferative, malignantand/or diseased tissue is selected from the group consisting of ahyperproliferative, malignant, and/or diseased epidermal, dermal, and/orhypodermal tissue.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the disclosure and many of the attendantadvantages thereof will be readily obtained as the same becomes betterunderstood by reference to the following detailed description whenconsidered in connection with the accompanying drawings, wherein:

FIG. 1a-d shows the (E) structure of light absorbing compounds (Ia, IIa,IIIa, IVa) comprising an oxadiazole isomer and a thiophene group. FIG.1a shows dye (a); FIG. 1b shows dye (IIa); FIG. 1c shows dye (IIa); andFIG. 1d shows dye (IVa).

FIG. 2 shows an absorption spectra of the (E) structure of each of lightabsorbing compounds (Ia, IIa, IIIa, IVa) comprising an oxadiazole isomerand a thiophene group.

FIG. 3 shows the structure of a dye sensitized solar cell incorporatingat least one light absorbing compound (Ia, IIa, IIIa, IVa) comprising anoxadiazole isomer and a thiophene group.

FIG. 4 shows an illustration of a dye having a chromophore coupled to aconjugated system.

FIG. 5 shows a schematic of a dye molecule having a donor group and anacceptor group separated by a spacer group.

DETAILED DESCRIPTION OF THE INVENTION

In a preferred embodiment the disclosure is drawn to a light absorbingmolecule of the D-π-A (Donor-spacer-Acceptor) type incorporating anoxadiazole moiety. The light absorbing molecule is preferably for use ina photovoltaic device, such as a dye-sensitized solar cell, or for usein photodynamic therapies.

The term ‘light absorbing molecule as used herein is meant to beinterchangable with the term ‘light absorbing compound’ and both ofthese terms as presented herein are meant to be interchangable with theterm photosensitizer.

The term “anchoring group”, as used herein, is meant to refer to anyfunctional group that allows a covalent coupling, which may also bereferred to as chemisorption of the entity to which such anchoring groupbelongs, to a surface, for example the surface of a nanoporoussemiconductor layer within a solar cell.

A “chromophore” as used herein is functional group within a molecularstructure that is responsible for the light absorption. A “conjugatedsystem” as used herein is a heteroaromatic molecule or portion of amolecule having alternating double bonds and single bonds between atomcenters. The term “molecular structure”, as used herein, refers to thestructure of a molecule. For example, the “molecular structure of a dye”is the structure of the molecule of the dye. An “anchoring group” thatis included in the molecular structure of a dye forms part of themolecular structure.

Herein, a dye is referred to as being “chemisorbed” to a layer orsurface, if the dye is covalently coupled thereto. The term “covalentcoupling”, as used herein, is interchangeable with the term“chemisorption”.

The term “a dye including an anchoring group in its molecular structure”as used herein, may have more than one anchoring group(s) present withinthe structure.

The term “a molecule that is able to absorb in the wavelength range ofUV and/or visible and/or IR light” as used herein, refers to a moleculethat is able to absorb light in one or in several regions of thewavelength range(s) indicated, or furthermore, over the total regions ofthe given wavelength range(s). For example a molecule may absorb in therange of from 250 nm-500 nm, whereas another molecule may absorb in therange of from 700 nm-1000 nm, whereas a third molecule may absorb in therange of from 250-1000 nm.

The term photoelectric transformation element is meant to comprisematerials that allow photoelectric transformation, or conversion to takeplace in a device, such as a dye sensitized solar cell.

The light absorbing compounds disclosed herein are characterized by thepresence of an electron-donating group (D) at one end of the dyecompound, and an electron-accepting group (A) at the other end of thedye compound, where (A) and (D) are linked by a π conjugated system. Theintroduction of a strong electron-withdrawing group such as acyanoacrylate group into the electron-donating backbone of the lightabsorbing compound results in a longer wavelength absorbance by loweringthe LUMO level to thereby desirably provide a high photoelectricconversion efficiency.

The light absorbing compounds are designed and prepared by introducingan oxadiazole group as a π-conjugated bridge between donor and acceptormoieties. In the resulting light absorbing compounds a biphenyl unitacts as an electron-donating moiety and carboxyl and cyano groups (—COOHand —CN) act as electron acceptor and anchor groups, respectively.

Referring now to the drawings, wherein like reference numerals designateidentical or corresponding parts throughout the several views.

FIG. 1a shows the (E) structure of dye (Ia) comprising an oxadiazoleisomer and a thiophene group. FIG. 1b shows the (E) structure of dye(IIa) comprising an oxadiazole isomer and a thiophene group. FIG. 1cshows the (E) structure of dye (IIIa) comprising an oxadiazole isomerand a thiophene group. FIG. 1d shows the (E) structure of dye (IVa)comprising an oxadiazole isomer and a thiophene group.

The dye molecules as disclosed herein have a donor group and an acceptorgroup separated by a spacer group (See FIG. 5), including the tautomersthereof:

where * in FIG. 5 indicates the oxadiazole structures as shown below:

Other portions of the light absorbing compound include:

The structure of the light absorbing compound is shown below. The lightabsorbing compound may have an (E) or (Z) configuration, including thetautomers thereof:

wherein A₁ is a divalent thiophene group of formula (I′)

wherein R₁ is H, OH, CH₃, Cl, Br, F, or I, and n=0-5, and n ispreferably 1;A₂ is at least one divalent 5-membered heterocyclic group of formulas(II′), (II′), (IV′), and (V′):

wherein m=1-5;A₃ is an aromatic hydrocarbon chromophore of formula (VI′)

wherein R₁ is H, OH, CH₃, Cl, Br, F, or I and p=1-3, and wherein thegroup A₃ of the light absorbing compound at a terminal position includesan aryl group bonded to one other aryl group and a hydrogen atom.

Each of the light absorbing compounds of the present disclosurecomprises at least one an anchoring group independently selected fromthe group consisting of —COOH, —SO₃H, —PO₃H₂, and —BO₂H₂, preferably—COOH. In one embodiment, the anchoring group is capable of bonding to asemiconductor electrode surface of an organic solar cell;

Each of the light absorbing compounds of the present disclosure alsocomprise an acceptor site selected from the group consisting of H, —CN,and —NO₂, preferably —CN. Together, these groups advantageously form acyanoacrylate group that attracts electrons by an inductive effect.

The π-conjugated spacer comprises at least one divalent 5-memberedheterocyclic oxadiazole group. In one embodiment a divalent thiophenegroup is also present. These groups may be represented by the formula:-(A¹-)-(-A²)-, wherein A¹ and A² each independently represent thethiophene and oxadiazole substituents, respectively. Furthermore, theπ-conjugated spacer has, as a constituent atom thereof, a heteroatomthat forms a double bond with carbon in the end region—on the side ofthe anchor backbone—and is bonded thereto.

According to the present disclosure, the donor group comprises anaromatic hydrocarbon as a chromophore. In one embodiment, the aromatichydrocarbon chromophore is a biphenyl group.

The compounds of the present disclosure may also be described as a dyehaving a chromophore coupled to a conjugated system (see FIG. 4) whereinthe chromophore is an organic molecule able to absorb UV and/or visiblelight when coupled with a conjugated system selected from the groupincluding and/or consisting of:

wherein p is 1-3, R₁ is H, OH, CH₃, Cl, Br, F, or I, and wherein thegroup A₃ of the chromophore has an aryl group bonded to one other arylgroup and a hydrogen atom at a terminal position;

wherein the conjugated system comprises a divalent thiophene group offormula (I′)

wherein R₁ is H, OH, CH₃, Cl, Br, F, or I, and n=0-5;

and at least one divalent 5-membered heterocyclic group of formula(II′), (III′), (IV′) and/or (V′)

wherein m=1-5;

wherein R₂ is selected from the group consisting of H, —CN, and —NO₂,preferably —CN, and

wherein R₃ is selected from the group consisting of —COOH, —SO₃H,—PO₃H₂, and —BO₂H₂, preferably —COOH.

Preferably the light absorbing compounds are not substituted with anyprimary, secondary or tertiary amine.

The light absorbing compounds and/or chromphores may simply be referredto as the compounds of the present disclosure.

The compounds of the present disclosure present a low H-L gap energy, inaddition to having a donor site comprising an electron-donating backboneat a location away from the anchor site. The oxadiazole structuralsystem of the compounds provide coordination bonds which improve theplanarity of the π-conjugated backbone, thus providing the compounds ofthe present disclosure with favorable properties as organic dye materialfor a dye-sensitized solar cell.

The compounds of the present disclosure include:

It is within the scope of this disclosure to combine at least two of thelight absorbing compounds with each other, such that a broader range ofthe solar spectrum may be harvested. Therefore mixtures of the dyes ofthe present disclosure when in use together will have absorption maximaat different wavelengths. In one embodiment, the dyes are mixed in aratio of 1:1, 1:2, or 1:3 parts per weight %.

A dye sensitized solar cell comprising two or more dyes, may be referredto as a multiple-dye sensitized solar cell (M-DSSC). In one embodiment,the M-DSSC device may be built in a tandem geometry wherein the dyes arenot mixed, but each is individually coated on at least two separatenanoporous layers and used in the device in at least two separatecompartments.

At least one a dispersing medium may be used with the light absorbingcompounds of the present disclosure. The dispersing medium may comprisean organic solvent selected from the group consisting of, but notlimited to pentane, hexane, octane, benzene, toluene, xylene, diethylether, methanol, ethanol, isopropanol alcohol, acetone, ethyl acetate,butyl acetate, methyl ethyl ketone, acetonitrile, nitriles,propionitrile, dimethyl sulfoxide, triethylamine, acetic acid, propionicacid, methylene chloride, chloroform, and tetrahydrofuran,

Studies were carried out to elucidate the role of the oxadiazole-basedmetal free photosensitizers and assist in the identification ofadditional organic dyes for DSSCs. The performance of each dyecomprising a different oxadiazole isomer as a π-conjugated bridge wasanalyzed. DFT/TD-DFT calculations were performed using Amsterdam DensityFunctional (ADF) program 2013.01 to investigate the key parameters oflight harvesting efficiency (LHE), free energy for electron injection(ΔG^(inject)), excitation energies, and frontier molecular orbitals(FMOs).

Results from the studies indicate that the light absorbing molecules ofthe present disclosure will exhibit a more negative ΔG^(inject)concurrent with having a high LHE value. These parameters indicate thatthe molecules demonstrate a desirable IPCE, or incident photon tocurrent efficiency.

Mechanisms of use and function may involve the direct attachment of thedye to a semiconductor surface, such as the TiO₂ surface, via the —COOHgroup of the cyanoacrylic group. The —CN group, having an electronacceptor character, positively effects electron injection from the dyeto the semiconductor. Molecular orbital calculations indicate that inthe ground state, the electron density is localized on the biphenylgroup, located far away from the semiconductor surface. The biphenylgroup is responsible for the light absorption abilities of the entiredye molecule. Furthermore, the theoretical HOMO of each of the series ofcompounds as disclosed herein is localized on the biphenyl group,whereas the LUMO is localized on the cyanoacrylic acid group. Electronicdistribution over the oxadiazole unit, and in one embodiment, theadditional thiophene unit, in both HOMO and LUMO shows that an effectivephotodriven charge transfer excitation can take place through thisplanar bridge. The electronic distribution of the HOMO and LUMO levelsare well separated and the transition between these two can beconsidered as a charge transfer excitation.

Additional calculations were performed to illustrate the oscillatorstrength of the proposed compounds, shown in FIG. 2. In spectroscopy,oscillator strength is defined as a dimensionless quantity thatexpresses the probability of absorption or emission of electromagneticradiation in transitions between energy levels of an atom or molecule.

The examples below are intended to further illustrate the variousembodiments of the oxadiazole-containing dyes, and are not intended tolimit the scope of the claims.

Example 1

The performance of DSSCs evaluated by IPCE:

IPCE is associated with charge collection efficiency (η_(c)), electroninjection efficiency (φ_(injc)) and light harvesting efficiency (LHE),as:IPCE=LHE×φ_(injc)×η_(c)  (1)LHE can be calculated in the following way:LHE=1−10^(−f)  (2)

where “f” is the absorption of dye associated with maximum absorptionalso called oscillator strength and φ_(injc) is related to the freeenergy of electron injection as:φ_(injc) αf(−ΔG ^(inject))  (3)Eq-3 shows that the more negative ΔG^(inject), the greater the electroninjection efficiency. ΔG^(inject) is the difference between theoxidation potential energy of the excited state (E_(ox) ^(dye)*) and thereduction potential energy of the TiO₂ conduction band (E_(CB)), whichcan be described as:ΔG ^(inject) =E _(ox) ^(dye) *−E _(CB)  (4)Similarly, E_(ox) ^(dye)* can be calculated using the followingequation:E _(ox) ^(dye) *=E _(ox) ^(dye) −ΔE  (5)

where E_(ox) ^(dye) (-HOMO) is the dye ground state oxidation potentialand ΔE is the lowest absorption energy associated with λ_(max).

Computational Detail

All DFT/TD-DFT calculations were performed using the Amsterdam DensityFunctional (ADF) program (2013.01). The ground state geometries of eachof the series of oxadiazole dyes were optimized by applying the hybridB3LYP level together with a triple-ζ polarization basis function. TheUV-Vis spectrum of each of the series of oxadiazole dyes was simulatedin an ethanol solvent. The conductor-like screening model (COSMO) wasutilized to take into account any effects attributable to the solvent.Excitation energies were examined using both TD-DFT and the statisticalaverages of orbital potentials (SAOP) models. These examination modelsalso took into account any effects attributable to the solvent system.In all the calculations, the relativistic effects were taken intoaccount by the zero order regular approximation (ZORA) Hamiltonian inits scalar approximation. As understood, the zeroth order regularapproximation (ZORA) to the Dirac equation accurately and efficientlytreats relativistic effects in chemistry. ZORA can be applied withspin-orbit coupling or as scalar correction only.

Designed Oxadiazole-Based Dyes

The structures of the oxadiazole-containing dyes are shown in FIG. 1. Inthese structures, a biphenyl group is designated as theelectron-donating moiety, and carboxyl and cyano groups (—COOH and —CN)are electron acceptor and anchor groups due to theirelectron-withdrawing ability and bonding ability, respectively.Oxadiazole isomers were each individually introduced as π-conjugationgroups in order to bridge the donor-acceptor systems. A double bond anda thiophene unit were also introduced to the π-conjugation system forthe fine tuning of molecular planar configurations, and to broaden theabsorption spectra of the dye molecules.

Initial quantum-chemical calculations using density functional theoryand time dependent density functional theory (DFT/TDDFT) indicate thatthe oxadiazole compound as disclosed maintain a planar geometry in theground state that, together with the position of the biphenyl moietyfavors efficient π-π stacking of the acceptor molecules and enhances theelectron mobility in the π-π direction. As a solvent, common organicsolvents such as water, but preferably ethanol, methanol, and butanol,may be used. For the theoretical calculations, ethanol was used as thetheoretical solvent.

Table 1 shows the HOMOs, LUMOs and HOMO-LUMO energy gaps of thecompounds of the disclosure. As previously discussed, the HOMO, LUMO,and band gap energies of photosensitizers play important roles inproviding the thermodynamic driving force for electron injection. Inorder to obtain an efficient charge transfer, the LUMOs of the dye mustbe more negative than the conduction band of the semiconductor, whilethe HOMO level must be more positive than the redox potential of theelectrolyte. These results obtained from the computational studiessuggest that each of the dye comprising the (E) enantiomer of theoxadiazole isomer dye further comprising a thiophene group of formulaIa, IIa, IIIa, and IVa are capable of injecting electrons into theconduction bands of TiO₂.

TABLE 1 The FMO (eV) and H-L _(gap) (eV) energies of Systems 1-4 DyesLUMO HOMO H-L_(GAP) Ia −3.867 −5.682 1.815 IIa −3.630 −5.508 1.878 IIIa−3.762 −5.865 2.103 IVa −3.882 −5.919 2.037

TABLE 2 The ground state potential E_(ox) ^(dye) (eV), excited statepotential E_(ox) ^(dye)* (eV), lowest absorption energy ΔE (eV), maximumabsorption λ_(max) (nm), oscillating strength (f) and transitioncharacter Dyes E_(ox) ^(dye) E_(ox) ^(dye)* ΔE λ_(max) f Main TransitionIa 5.682 3.482 2.3 540 0.59 H → L (96%) IIa 5.508 3.308 2.2 565 0.58 H→L + 1(60%) IIIa 5.865 3.765 2.2 561 0.72 H-1 →L (86%) IVa 5.919 3.7192.2 563 0.71 H → L (95%)

LHE and ΔG^(inject) can be calculated by using equation-2 and equation-4respectively. The results are tabulated in Table 3. It can be found fromTable 3 that all the ΔG^(inject) values calculated are negative,indicating that the conduction band edge of TiO₂ lies below the excitedstate of the dyes, and thus favors the electron injection. Asillustrated in Table 3, there is only a slight difference in the LHEvalues between Dyes Ia-IVa, indicating that each of the photosensitizersas disclosed herein all generate comparable photocurrent values.

TABLE 3 Free energy of electron injection ΔG^(inject) (eV) and Lightharvesting efficiency LHE Dyes ΔG^(inject) LHE Ia −0.613 0.738 IIa−0.692 0.740 IIIa −0.335 0.801 IVa −0.281 0.796

The simulated absorption spectra of Dyes Ia-IVa are shown in FIG. 1. Theabsorption spectra of each dye comprises two regions consisting of afirst intense peak in the region of 326 nm-500 nm and second peak in theregion of 472 nm-700 nm. The dye comprising the 1, 2, 3 oxadiazolebridge displays a broader peak when compared to the dyes comprising theremaining oxadiazole isomers in the series of dyes. The ground andexcited state potential (E_(ox) ^(dye)), maximum absorption (λ_(max))oscillation strength (f) and main transitions are all presented in Table2.

The DSSC of the present disclosure comprises at least one of theoxadiazole dyes, an anode, a cathode, and an electrolyte. The anode andcathode are arranged in a sandwich-like configuration, and theelectrolyte is inserted between the two electrodes. A DSSC incorporatingat least one of the series of light absorbing molecules, or lightabsorbing photosensitizers, is shown in FIG. 3.

The cathode 39 comprises an electrically conductive substrate, such as atransparent glass comprising an oxide selected from the group consistingof, but not limited to, titanium dioxide, zinc oxide, tin oxide, orindium-tin oxide (ITO).

The anode comprises an electrically conductive substrate, such as atransparent glass and a semiconducting layer comprising a semiconductor33 and at least one oxadiazole-containing dye 35 adsorbed thereto.Materials for the semiconductor include, but are not limited to, metaloxides such as titanium oxides, niobium oxides, zinc oxides, tin oxides,tungsten oxides, TiOF₂, and indium oxides, preferably TiO₂, while anelectrolytic solution 37 is generally based on an iodine redox couple(I⁻/I₃ ⁻). Light is supplied from a light source, such as the sun 31 andtransformation of solar energy to electrical energy is shown by thearrow 41 (FIG. 3).

The light absorbing oxadiazole compounds as disclosed herein arepreferably adsorbed onto the semiconductor via contact of the dye. Thedye and the semiconductor surface maintain contact through a chemicalbond between the anchoring group of the dye and the semiconductormaterial.

Any aggregation of the dye molecules may reduce the efficiency of theDSSC. Therefore, in one embodiment, it is desirable to include a bulkychemical compound in the dye solution to improve the solubility of thedye, and to prevent dye molecules from aggregating. Chemical groups canbe selected from the group consisting of, but not limited to, thecompounds of the current disclosure without their binding anchor group.

Further advantages include the tuning or selection of the dye indetermining the wavelength of light that the solar cell (e.g., DSSC) cancapture. Any adjustment to the dye structure and/or color will influencethe performance of the device. Many dyes reflect red light, and, whencoupled with an oxide such as titanium oxide (white), appear ‘pink’.However, the series of light absorbing molecules as disclosed hereinabsorb light in several ranges so there exists the possibility ofchoosing a different coloring of the dye sensitized solar cell device inrelation to the application type.

The use of the light absorbing molecules of this disclosure as dyes indye sensitized solar cell applications include a variety of electronicdevices. These devices include energy supply devices for mobile phones,notebooks, laptops, portable audio-tape players, MP3-players, remotecontrols, e-cards, e-books, e-readers, portable CD players, portable DVDplayers, cameras, digicams, GPS devices, portable sensors, and portablesolar chargers for batteries of any of the aforementioned devices. Asorganic dyes have high absorption coefficients, a lesser amount of dyeis able to absorb the same amount of light. A lower, or lesser amount ofone dye on a surface enables the use of more dyes with differentabsorption properties, ideally being a mixture of dyes absorbing theentire range of the solar spectrum.

The compounds of the current disclosure may have further application inthe field of photodynamic therapy. The light absorbing compoundsdisclosed herein contain few atoms and absorb in the longer wavelengthregions thus providing for use in photodynamic therapies for thetreatment of malignant, diseased, hypo- and/or hyper-proliferative cellsand/or tissues. Formulations or compositions comprising at least one ofthe light absorbing compounds disclosed herein may act as aphotopharmaceutical for treating conditions such as, but not limited tocancer, benign tumors, skin infections, and even a lack or reduction ofhair growth.

During a photodynamic therapy (PDT) treatment, at least one of the lightabsorbing compounds may be supplied to an area of the body in need oftreatment. The area is then exposed to light of a suitable frequency andintensity necessary to activate the photopharmaceutical so as to causenecrosis, or apoptosis of the targeted tissue. In a further embodiment,a stimulation of a hypo-proliferative tissue may occur.

Administration of Photosensitizers

The light absorbing compounds may be administered as a topical orsubcutaneous preparation, or by localized administration in the form ofan intradermal injection or an implant. The light absorbing compoundsmay be administered by means including, but not limited to, topicallotions, topical creams, topical pastes, topical suspensions, or a localadministration in the form of intradermal injection or an implant. Apreferred method of administration is to apply the light absorbingcompounds topically in an excipient containing a solubilizing agent. Fortopical formulations (such as ointments) to be applied to the surface ofthe skin, the concentration of the light absorbing compound in theexcipient preferably ranges from about 0.001 to about 10% w/w, and morepreferably from about 0.005 to about 5% w/w, and even more preferablybetween about 0.01 to about 1% w/w. Particularly preferred is the use ofabout a 0.2% w/w topical formulation.

The dose of light absorbing compound may be determined by factors suchas, but not limited to, the light absorbing compound chosen, thephysical delivery system in which it is carried, the individual subject,and the target tissue to be treated. The dose should also be adjustedwith respect to parameters, such as irradiance, duration of the lightused in PDT, and time interval between administration of the dose andthe therapeutic irradiation. Depending on the specificity of thepreparation, smaller or larger doses of photosensitizers may be needed.For compositions which are highly specific to the target skin tissuesand cells. The potency of the light absorbing compound also determinesthe dosage, with less required for highly potent light absorbingcompounds, and more for light absorbing compounds with less potency. Fortopical formulations (such as ointments) to be applied to the surface ofthe skin, the concentration of the light absorbing compound in theexcipient can range from about 0.001 to about 10% w/w, preferably fromabout 0.005 to about 5% w/w (or about 0.05 to about 1% w/w), and evenmore preferably between about 0.1 to about 1% w/w.

Each light absorbing compound requires activation with an appropriatewavelength(s) of electromagnetic radiation. As such, the methods of theinvention may be conducted with any irradiation, preferably with light,which activates the light absorbing compound used. Preferably, theirradiation contains one or more wavelength which is capable ofpenetrating the skin to activate the light absorbing compound used. Thewavelength(s) of radiation or light useful in the invention depends onthe activation range of the light absorbing compound used as part of thetreatment method. In one embodiment the wavelengths range from 326-700nanometers (nm). Depending upon the light absorbing compound and uponthe desired depth of targeted tissue penetration, the preferredwavelengths range from about 500 to about 700 nm. The oxadiazole lightabsorbing compounds may be activated by a red light, as well as ambientlight containing wavelengths from 326 nm-700 nm. Light having awavelength shorter than 400 nm may be considered acceptable, but notpreferred because of the potentially damaging effects of UVA light.

Any appropriate activation energy source, depending on the absorptionspectrum of the light absorbing compound, may be used for activation.Preferred sources include, but are not limited to, lasers, lightemitting diodes (LED), incandescent lamps, arc lamps, standardfluorescent lamps, U.V. lamps, and combinations thereof. More preferredare lasers, light emitting diodes, and combinations thereof

Alternatively, any convenient source of activation energy having acomponent of wavelengths that are absorbed by the light absorbingcompound may be used, for example, an operating room lamp, or any brightlight source, including sunlight. Wavelengths in the ultraviolet rangeare not preferred as they may lead to a mutagenic event. Therefore, theactivation energy used for the methods herein is not in the ultravioletrange.

The activation energy dose administered during the PDT treatmentcontemplated herein can vary as necessary. Preferably, for lightabsorbing compounds of high potency, the dosage of the light isapproximately 25-200 J/cm² for a topically-delivered photosensitizers.It is recommended that the total dose of the irradiation should notexceed 200 J/cm², more preferably not to exceed 100 J/cm². Foradministering the light absorbing compound the preferred doses can rangebetween about 0.01 J/cm² to about 200 J/cm², more preferably 0.1 J/cm²to about 100 j/cm². Increases in irradiance will generally decrease thelight exposure times. Generally, a higher dose of photosensitizer willalso decrease the light dose required to exert a therapeutic effect.

The intensity of the light source should not exceed about 600-1000mW/cm². Irradiances between about 10 and about 400 mW/cm², arepreferred; more preferably are those between about 25 and about 100mW/cm².

The irradiation may last from about 10 seconds to about 3 hours,preferably between 1 minute and 90 minutes. Irradiation times of between5 minutes and 10 minutes may be used. The irradiation or light exposureas disclosed may be directed to a small or large area of the body orscalp depending on the tissue to be treated. Treatment may be precededwith an assessment of the time of light exposure for the patient'sminimal erythemal dose (MED) occurrence in order to avoid potentialburning of the exposed skin.

The PDT may be a single treatment, but it is preferred that thetreatment is repeated. The frequency may vary. For example, thetreatments may be daily, twice weekly, weekly, every two weeks, monthly,every six weeks, every two months, quarterly, twice annually, orannually, or other suitable time interval to treat or maintain atargeted tissue's prevailing condition. The total number of treatmentsof a specifically targeted tissue can range from one to twenty. In caseswhere hair loss is observed, maintenance treatment on a regular basismay be initiated and sustained. It is preferred that the total number oftreatments in any one-month period be from 1 to 12, more preferably from2 to 4.

The time between administration of light absorbing compound andadministration of activation energy will vary depending on a number offactors. Activation energy delivery can take place at any suitable timefollowing administration of light absorbing compound as long as there isstill light absorbing compound present at the skin. Activation energytreatment within a period of about five minutes to about 5 hours afteradministration of the light absorbing compound is preferred, with arange of 15 minutes to 90 minutes being more preferable. Even morepreferably the light is administered within a period of about 30-45minutes after administration of the light absorbing compound. Lightabsorbing compounds that may rapidly accumulate in target tissues can beactivated soon after administration. Also, light absorbing compoundsthat may be metabolically cleared from tissues quickly should beactivated soon after accumulation in the target tissues.

The light absorbing compounds disclosed herein may be formulated into avariety of compositions. These compositions may comprise any componentthat is suitable for the intended purpose, such as conventional deliveryvehicles and excipients including isotonising agents, pH regulators,solvents, solubilizers, dyes, gelling agents and thickeners and buffersand combinations thereof. Suitable excipients for use with lightabsorbing compounds include water, saline, dextrose, glycerol and thelike.

Typically, the light absorbing compound is formulated by mixing it, atan appropriate temperature, e.g., at ambient temperatures, and atappropriate pHs, and the desired degree of purity, with one or morephysiologically acceptable carriers, i.e., carriers that are nontoxic atthe dosages and concentrations employed. The pH of the formulationpreferably ranges anywhere from about 3 to about 8, preferably in thephysiological range of 6.5 to 7.5.

The formulations may comprise a skin-penetration enhancer selected fromthe group consisting of glycol ethers, fatty acids, fatty acid esters,glycol esters, glycerides, azones, polysorbates, alcohols,dimethylsulfoxide, and mixtures thereof.

Solvents acceptable for use in the treatment include, but are notlimited to, DMSO (dimethylsulfoxide), polyethylene glycol (PEG),ethanol, and methyl alcohol, while solubilizers such as, but not limitedto titanium dioxide, polyethylene glycol, propylene glycol,polysorbates, and mixtures thereof may also be added at a percentage of10% to 70% by weight.

It is preferred that the formulations have a viscosity at 20° C. of fromabout 50 cps to about 50000 cps, more preferably from about 500 cps toabout 40000 cps, even more preferably from about 5000 cps to about 30000cps. Viscosity modifiers can be selected from the group consisting ofbut not limited to polyethylene glycols, waxes, saturated C₈-C₁₈ fattyacid glycerides, xantham gum, polyvinyl alcohol, and mixtures thereof.

Thus, the foregoing discussion discloses and describes merely exemplaryembodiments of the present invention. As will be understood by thoseskilled in the art, the present invention may be embodied in otherspecific forms without departing from the spirit or essentialcharacteristics thereof. Accordingly, the disclosure of the presentinvention is intended to be illustrative, but not limiting of the scopeof the invention, as well as other claims. The disclosure, including anyreadily discernible variants of the teachings herein, defines, in part,the scope of the foregoing claim terminology such that no inventivesubject matter is dedicated to the public.

The invention claimed is:
 1. A dye sensitized solar cell, comprising: ananode, a cathode, an electrolyte between the anode and the cathode, alight absorbing layer comprising a semiconductor and a light absorbingcompound, wherein the light-absorbing compound is chemisorbed on thesemiconductor; and wherein the light absorbing compound has formula (I):

wherein A₁ is a divalent thiophene group of formula (I′)

A₂ is a divalent 5-membered heterocyclic group of at least one offormula (II′), (III′), (IV′), and (V′):

A₃ is an aromatic hydrocarbon chromophore of formula (VI′)

wherein R₁ is H, OH, C1-C6 alkyl, Cl, Br, F, or I, p is from 1-3, m isfrom 1-5, and n is from 0-5.
 2. The dye sensitized solar cell of claim1, wherein the light absorbing compound of the formula (I) is an (E)isomer.
 3. The dye sensitized solar cell of claim 1, wherein the lightabsorbing compound of the formula (I) is a (Z) isomer.
 4. The dyesensitized solar cell of claim 1, wherein the light absorbing compoundis at least one selected from the group consisting of(E)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylicacid;(E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylicacid;(E)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylicacid;(E)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylicacid;(E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylicacid;(E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylicacid;(E)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylicacid;(E)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylicacid; and(Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)-2-cyanoacrylicacid;(Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)-2-cyanoacrylicacid;(Z)-3-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)-2-cyanoacrylicacid;(Z)-3-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)-2-cyanoacrylicacid;(Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,3,4-oxadiazol-2-yl)thiophen-2-yl)-2-cyanoacrylicacid;(Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,3-oxadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylicacid;(Z)-3-(5-(5-([1,1′-biphenyl]-4-yl)-1,2,4-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylicacid; and(Z)-3-(5-(4-([1,1′-biphenyl]-4-yl)-1,2,5-oxadiazol-3-yl)thiophen-2-yl)-2-cyanoacrylicacid.
 5. The dye sensitized solar cell of claim 1, wherein the lightabsorbing compound is represented by formula (Ia)


6. The dye sensitized solar cell of claim 1, wherein the light absorbingcompound is represented by formula (Ib)


7. The dye sensitized solar cell of claim 1, wherein the light absorbingcompound is represented by formula (IIa)


8. The dye sensitized solar cell of claim 1, wherein the light absorbingcompound is represented by formula (IIb)


9. The dye sensitized solar cell of claim 1, wherein the light absorbingcompound is represented by formula (IIIa)


10. The dye sensitized solar cell of claim 1, wherein the lightabsorbing compound is represented by formula (IIIb)


11. The dye sensitized solar cell of claim 1, wherein the lightabsorbing compound is represented by formula (IVa)


12. The dye sensitized solar cell of claim 1, wherein the lightabsorbing compound is represented by formula (IVb)